直接观察芳基碳-氧键向钌配合物的氧化加成反应，并考虑芳基碳-氧键与芳基碳-氢键之间的相对反应活性。

Direct observation of the oxidative addition of the aryl carbon-oxygen bond to a ruthenium complex and consideration of the relative reactivity between aryl carbon-oxygen and aryl carbon-hydrogen bonds.

作者信息

Ueno Satoshi, Mizushima Eiichiro, Chatani Naoto, Kakiuchi Fumitoshi

机构信息

Department of Chemistry, Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama, Kanagawa 223-8522, Japan.

出版信息

J Am Chem Soc. 2006 Dec 27;128(51):16516-7. doi: 10.1021/ja067612p.

DOI:10.1021/ja067612p

PMID:17177397

Abstract

When RuH2(CO)(PPh3)3 was reacted with 2,2-dimethyl-1-(2-p-tolylphenyl)propan-1-one (2), the ruthenium-aryloxy complex 3 was obtained in 76% yield. The structure of this complex was determined from 1H and 31P NMR and X-ray data. Complex 3 showed the catalytic activity for the coupling of 2 with the phenylboronate 4. The 1H and 31P NMR studies of the reaction of Ru(CO)(PPh3)3 with o-aryloxy pivalophenone revealed that the C-H bond cleavage is a kinetically favorable process but the C-O bond cleavage is a thermodynamic one. The reaction of 2'-methoxyacetophenone with vinylsilane and organoboronate resulted in chemoselective C-C bond formation.

摘要

当RuH2(CO)(PPh3)3与2,2-二甲基-1-(2-对甲苯基苯基)丙-1-酮(2)反应时，以76%的产率得到钌-芳氧基配合物3。该配合物的结构通过1H和31P NMR以及X射线数据确定。配合物3对2与苯基硼酸酯4的偶联反应显示出催化活性。对Ru(CO)(PPh3)3与邻芳氧基新戊苯乙酮反应的1H和31P NMR研究表明，C-H键断裂是动力学上有利的过程，而C-O键断裂是热力学过程。2'-甲氧基苯乙酮与乙烯基硅烷和有机硼酸酯的反应导致了化学选择性C-C键的形成。